Solid catalyst component and catalyst for olefin polymerization, process for producing olefin polymer and process for producing solid catalyst component

ABSTRACT

There are disclosed: 
     (i) a first solid catalyst component (A1) obtained by contacting (a) a carrier of carboxyl group-carrying polymer particles having an average particle size of from about 1 to 200 μm, (b) an organometallic compound of the number 1, 2 or 13 group of metals in the periodic table of elements, and (c) a transition metal compound of the number 4 group of metals of the periodic table of elements, and a second solid catalyst component (A2) obtained by contacting (a), (b), (c) and (d) a phenol compound, and production processes of the solid catalyst components (A1) and (A2), 
     (ii) a catalyst obtained by combining the solid catalyst component (A1) or (A2) with an organoaluminum compound (B); and 
     (iii) a process for producing an olefin polymer with a catalyst of the invention, wherein the polymer produced is extremely low in its content of lower molecular weight components and low crystallinity components, and superior in its powder properties.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. Ser. No.09/281,212, filed Mar. 30, 1999, now U.S. Pat. No. 6,468,937, the entiredisclosure of which is incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to a solid catalyst component and acatalyst for olefin polymerization, which are high in theirpolymerization activity and capable of producing an olefin polymerextremely low in its content of lower molecular weight components andlow crystallinity components and superior in its powder properties. Theinvention also relates to a process for producing an olefin polymer, anda process for producing the solid catalyst component,

BACKGROUND OF THE INVENTION

As a catalyst for olefin polymerization, a Ziegler-Natta catalystcomposed of a combination of a transition metal component and anorganometal component is well known, and as a high activity catalyst forolefin polymerization, there are proposed many catalysts, for example,those comprising an organoaluminum compound and a solid catalystcomponent obtained by using a titanium compound and a magnesiumcompound.

However, these catalysts leave problems such that when they are used forthe polymerization of α-olefins such as propylene or thecopolymerization of ethylene with α-olefins, the resulting polymercontains a lot of lower molecular weight components and lowcrystallinity components which affect a transparency, an impactresistance and a blocking property of the film or sheet obtained bymolding the polymer.

With respect to the polymerization of α-olefins such as propylene, thereare proposed a process comprising incorporating an electron donor suchas esters and ethers as an internal donor into a solid catalystcomponent, and a process comprising incorporating an electron donor suchas esters, ethers, amines and organosilicone compounds, as an externaldonor into a catalyst composed of a solid catalyst component and anorganoaluminum compound, whereby the stereospecificity of the resultingpolymer is improved to decrease the lower molecular weight componentsand the low crystallinity components contained in the polymer. Whereas,with respect to the copolymerization of ethylene with α-olefins, thereare also proposed processes of decreasing the lower molecular weightcomponents and the low ctystallinity components contained in the polymerby using electron donors as the internal or external donor.

However, in the polymerization of α-olefins such as propylene, or thecopolymerization of ethylene with α-olefins, such processes of usingelectron donors as the internal or external donor are not alwayssatisfactory from a viewpoint of decreasing the production of lowermolecular weight components and low crystallinity components.

Meanwhile, in the olefin polymerization, it is desired that theresulting powder polymer is superior in its powder properties, that is,high in its bulk density, narrow in its particle size distribution andsuperior in its flowability, from a viewpoint of an operationalstability and operational efficiency.

In recent years, as a new solid catalyst component, there is known asolid catalyst component obtained by fixing a magnesium compound and atitanium compound on a carrier of a functional group-carrying polymer.For example, WO 94/20545 and U.S. Pat. No. 5,409,875 disclose a processfor polymerizing ethylene, wherein an organic solvent solution of anethylene/unsaturated carboxylic acid copolymer is mixed with a poorsolvent to precipitate the copolymer, followed by pulverization to forma carrier, and the carrier is contacted with an organomagnesium compoundand a transition metal compound to obtain a solid catalyst component,which is used in combination with an organoaluminum compound for thepolymerization of ethylene.

The above catalyst obtained by using the carrier is described in thepatent specification to exhibit a high activity also in thecopolymerization of ethylene with α-olefins. However, the catalyst hasbeen found to be insufficient relating to the content of the lowermolecular weight components and the low crystallinity components in theresulting copolymer. Moreover, it has been found that the solid catalystcomponent obtained by using the carrier contains fine powders to make aparticle size distribution broad, and therefore it is not satisfactoryalso relating to the powder properties of the resultingethylene/α-olefin copolymer.

Each of the references referred to above is incorporated by reference inits entirety.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a solid catalystcomponent and catalyst for olefin polymerization, which are high intheir polymerization activity and capable of producing olefin polymersthat are extremely low in their content of lower molecular weightcomponents and low crystallinity components and that are superior intheir powder properties.

Another object of the present invention is to provide a process forproducing an olefin polymer.

A further object of the present invention is to provide a process forproducing the solid catalyst components of the invention.

The present inventors have undertaken extensive studies to accomplishtheir objects, and, as a result, have found that desired results can beobtained when a carrier of specific carboxyl group-carrying polymerparticles is used, and thereby the present invention has been obtained.

The present invention provides a solid catalyst component (A1) forolefin polymerization, which is obtained by contacting:

(a) a carrier of carboxyl group-carrying polymer particles having anaverage particle size of from about 1 to 200 μm,

(b) an organometallic compound of the number 1, 2 or 13 group of metalsin the periodic table of elements, and

(c) a transition metal compound of the number 4 group of metals in theperiodic table of elements,

The present invention also provides a solid catalyst component (A2) forolefin polymerization, which is obtained by contacting:

(a) a carrier of carboxyl group-carrying polymer particles having anaverage particle size of from about 1 to 200 μm,

(b) an organometallic compound of the number 1, 2 or 13 group of metalsin the periodic table of elements,

(c) a transition metal compound of the number 4 group of metals in theperiodic table of elements, and

(d) a phenol compound,

The present invention further provides a catalyst for olefinpolymerization, which is obtained by using any one of the aforementionedsolid catalyst components (A1) and (A2), and at least one compound (B)selected from the group consisting of organoaluminum compounds andorganoaluminumoxy compounds.

The present invention further provides a process for producing an olefinpolymer, which comprises utilizing said catalyst to catalyze a reactionbetween olefins, diolefins or a mixture thereof.

The present invention furthermore provides a process for producing thesolid catalyst components (A1) and (A2), which comprises contacting theaforementioned (a) to (c), or (a) to (d), respectively.

In the above, groups 1, 2 and 13 in the periodic table of elements arethose previously referred to as groups 1a, 2a and 3a, respectively. Thegroup 4 in the periodic table of elements is that previously referred toas group 4b.

DETAILED DESCRIPTION OF THE INVENTION

The following description is not to be construed as limiting the presentinvention, as those of ordinary skill in the art will realize thatvarious changes can be made in the various materials and procedurestaught herein, without departing from the spirit or scope of the presentinventive discovery. In this respect, the present invention is onlylimited by the scope of the claims appended hereto, and the equivalentsencompassed thereby. The present invention is explained in detail asfollows.

(a) Carrier

The carrier used in the present invention comprises polymer particlescontaining a polymer having a carboxyl group, and the polymer particleshaving an average particle size of from about 1 to 200 μm. The polymerparticles are preferably spherical or nearly spherical in their shape.Spherical or elliptical particles are particularly preferred. Thecarrier may be used singly or in a mixture of two or more kinds ofpolymer particles, and some other polymers may be admixed so far as theobjects and effects of the present invention are not impaired. The valuerelating to the average particle size of the polymer particles isobtained by measuring a slurry of the polymer particles in, for example,water or an alcohol with a particle size measuring apparatus such asCOULTER MULTISIZER.

The above polymer having a carboxyl group is not particularly limited.Preferred examples thereof are copolymers comprising carboxylgroup-carrying unsaturated monomer units and polymers imparted with acarboxyl group by any chemical or physical modification. The carboxylgroup-carrying unsaturated monomers include, for example, unsaturatedcarboxylic acids such as acrylic acid and methacrylic acid. Of these,acrylic acid is preferred.

Said copolymers comprising carboxyl group-carrying unsaturated monomerunits are not particularly limited. Preferred examples thereof arecopolymers of ethylene, propylene or styrene with unsaturated monomershaving a carboxyl group such as, for example, ethylene/acrylic acidcopolymer, ethylene/methacrylic acid copolymer, propylene/acrylic acidcopolymer, propylene/methacrylic acid copolymer, styrene/acrylic acidcopolymer and styrene/methacrylic acid copolymer.

Among these copolymers, those having ethylene, propylene or styreneunits as a main component are preferred. More preferred are those havingabout 49.9 to 0.1% by weight of carboxyl group-carrying unsaturatedmonomer units and about 50.1 to 99.9% by weight of ethylene, propyleneor styrene units, and much more preferred are those having about 30 to1% by weight of carboxyl group-carrying unsaturated monomer units andabout 70 to 99% by weight of ethylene, propylene or styrene units. Ofthese, copolymers having about 20 to 5% by weight of acrylic acid ormethacrylic acid units and about 80 to 95% by weight of ethylene unitsare specifically preferred.

Polymers to be imparted with a carboxyl group by any chemical orphysical modification are not particularly limited. Preferred examplesthereof are polymers having ethylene, propylene or styrene units. Morepreferred are homopolymers of ethylene, propylene or styrene, andcopolymers having ethylene, propylene or styrene units as a maincomponent, and much more preferred are (co) polymers having about 50.1to 100% by weight of ethylene, propylene or styrene units and about 49.9to 0% by weight of α-olefin units. Specific examples thereof arepolyethylene, ethylene/α-olefin copolymer, polypropylene,propylene/ethylene copolymer, propylene/butene-1 copolymer andpolystyrene.

The chemical or physical modification for imparting the carboxyl groupto the polymer may be any one known in the art. There are exemplified aprocess wherein a halogen-containing polystyrene such asstyrene/bromostyrene copolymer is treated with an organic alkali metalcompound such as n-BuLi and then the resulting product is subjected toreaction with carbon monoxide to obtain styrene/carboxylstyrenecopolymer, and a process wherein a polyolefin such as polypropylene anda carboxyl group-carrying unsaturated monomer is melt-kneaded in thepresence of an organic peroxide to obtain acrylic acid-modifiedpolypropylene. The carboxyl group-carrying unsaturated monomer used inthe latter process includes those mentioned above. Of these, acrylicacid and maleic anhydride are preferred. When acid anhydrides such asmaleic anhydride are used, it is recommendable to subject themelt-kneaded product to hydrolysis.

Specific examples of the polymer imparted with a carboxyl group by thechemical or mechanical modification are styrene/carboxylstyrenecopolymer, acrylic acid-modified polyethylene, acrylic acid-modifiedpolypropylene, acrylic acid-modified polystyrene, maleic acid-modifiedpolyethylene, maleic acid-modified polypropylene, maleic acid-modifiedpolystyrene, maleic anhydride-modified polyethylene, maleicanhydride-modified polypropylene, maleic anhydride-modified polystyreneand those obtained by hydrolysis of said maleic anhydride-modifiedpolymers.

An average particle size of the polymer particles for the carrier usedin the present invention is from about 1 to 200 μm, preferably fromabout 3 to 100 μm, more preferably from about 5 to 80 μm. A standarddeviation relating to the particle distribution of the polymer particlesis preferably from about 0.1 to 50 μm, more preferably from about 1 to30 μm, further preferably from about 3 to 20 μm. By using a carrier ofparticles having such a relatively uniform particle size, olefinpolymers can be obtained which are extremely low in their content oflower molecular weight components and low crystallinity components andsuperior in their powder property. In the above, the values relating tothe average particle size and the standard deviation of the particledistribution are by weight distribution.

The polymer particles used may be those commercially available or thoseobtained by dispersing carboxyl group-carrying polymers. A technique ofdispersing polymers is described in, for example, U.S. Pat. Nos.3,422,049 and 3,432,483. Each of these references is incorporated byreference in its entirety.

According to the above U.S. patents, a carboxyl group-carrying polymer,a polar solvent which does not completely dissolve said polymer and asurfactant are mixed with one another under stirring at a hightemperature, thereby obtaining polymer particles. In this respect, thetemperature is preferably not lower than a melting point of the polymer,providing that the polymer is not decomposed at that temperature, and apressure is usually from atmospheric to 250 atm. As the polar solventwhich does not completely dissolve the polymer, water and an aqueoussolvent mainly composed of water are particularly preferred. As thesurfactant, a block copolymer of ethylene oxide and propylene oxide isexemplified. The commercially available products mentioned above areusually those produced by this method.

Because the polymer particles are frequently contaminated withimpurities such as surfactants and those by-produced in the course ofthe polymerization, which affect the polymerization activity of thecatalyst, it is recommendable to wash the polymer particles with anorganic solvent to remove impurities prior to the practical use. Thecarrier of the polymer particles thus obtained has advantages such thatthe shape of the particles is maintained. In this respect, the carrierthus obtained can be differentiated from the carrier obtained by addinga bad solvent to an organic solvent solution of a copolymer toprecipitate the copolymer, and pulverizing the precipitated copolymer,as described in the aforesaid WO 94/20545 and U.S. Pat. No. 5,409,8753.The catalyst according to the present invention obtained using such acarrier is particularly high in its activity, and can give olefinpolymers that are low in their content of lower molecular weightcomponents and low crystallinity components and superior in their powderproperties.

The organic solvent used for washing the polymer particles is an organicsolvent which does not completely dissolve the polymer particles.Examples thereof are ketone solvents such as acetone, methyl ethylketone and methyl isobutyl ketone, nitrile solvents such asacetonitrile, aliphatic hydrocarbon solvents such as pentane, hexane,heptane, octane and decane, aromatic hydrocarbon solvents such asbenzene, toluene and xylene, alicyclic hydrocarbon solvents such ascyclohexane and cyclopentane, halogenated hydrocarbon solvents such as1,2-dichloroethane and monochlorobenzene, and ether solvents such asdiethyl ether and tetrahydrofuran. Among these, ketone solvents arepreferred, and acetone is particularly preferred from an economicalviewpoint.

The washing of polymer particles with the organic solvent can be carriedout preferably in a manner such that the polymer particles are slurriedwith the organic solvent at a temperature at which the polymer particlesare not completely dissolved and the shape thereof can be maintained,and after stirring for about 1 minute to 10 hours, the slurry isfiltered to separate the particles, which are then dried. The slurryingtemperature is usually from about −30 to 100° C., preferably from about0 to 80° C., more preferably from about 20 to 60° C., and the drying iscarried out preferably at about 5 to 60° C. for about 10 minutes to 10hours under reduced pressure.

(b) Organometallic Compound

The organometallic compounds used in the present invention are those ofa metal belonging to the 1, 2 or 13 group of elements in the periodictable of the elements. Among them, organometallic compounds of a metalbelonging to the 1 or 2 group are preferred. More preferred areorganomagnesium compounds and much more preferred aredihydrocarbylmagnesium compounds.

The 1 group metal of the periodic table includes, for example, lithium,sodium and potassium, and the organometallic compounds of said metalincludes, for example, hydrocarbyllithium, hydrocarbylsodium andhydrocarbylpotassium. Of these, hydrocarbyllithium compounds such asmethyllithium, ethyllithium and butyllithium are preferred.

The 2 group metal of the periodic table includes, for example, magnesiumand calcium, and the organometallic compounds of said metal includes,for example, dihydrocarbylmagnesium, hydrocarbylmagnesium halide anddihydrocarbylcalcium.

The dihydrocarbylmagnesium is represented by the following formula,

R¹R²Mg

wherein R¹ and R² may be the same and different, and denote ahydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon groupdenoted by R¹ and R² includes preferably alkyl, aryl, aralkyl andalkenyl groups, and specific examples thereof are methyl, ethyl,n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, iso-amyl, hexyl,octyl, 2-ethylhexyl, phenyl and benzyl groups. Of thesedihydrocarbylmagnesium compounds, diethylmagnesium,n-butylethylmagnesium and di-n-butylmagnesium are preferably used. Thesedihydrocarbylmagnesium compounds may be used in the form of a mixturewith a trialkylaluminum mentioned below.

The hydrocarbylmagnesium halides are in general called a Grignardreagent, and usually represented by the following formula,

R³MgY

wherein R³ is a hydrocarbon group having 1 to 20 carbon atoms, and Y isa halogen atom. Examples of the hydrocarbon group denoted by R³ aresimilar to those of R¹ and R². The halogen atom denoted by Y includes,for example, fluorine, chlorine, bromine and iodine atoms. Of these,chlorine and bromine atoms are preferred. Specific examples of thehydrocarbylmagnesium halides are methylmagnesium chloride,methylmagnesium bromide, methylmagnesium iodide, ethylmagnesiumchloride, ethylmagnesium bromide, n-butylmagnesium chloride,n-butylmagnesium bromide, cyclohexylmagnesium chloride, allylmagnesiumchloride, phenylmagnesium chloride, phenylmagnesium bromide, andbenzylmagnesium chloride. Of these, methylmagnesium chloride,methylmagnesium bromide, n-butylmagnesium chloride, n-butylmagnesiumbromide and phenylmagnesium chloride are preferred.

The 13 group metal of the periodic table includes, for example, aluminumand gallium, and the organometallic compounds of said metal includes,for example, organoaluminum, organoaluminum halides and organoaluminumhydrides. Examples of the organoaluminum are trimethylaluminum,triethylaluminum and triisobutylaluminum, examples of the organoaluminumhalides are dimethylaluminum chloride, dimethylaluminum bromide,diethylaluminum chloride, diisobutylaluminum chloride, methylaluminumdichloride, ethylaluminum dichloride, isobutylaluminum dichloride andethylaluminum sesquichloride, and examples of the organoaluminumhydrides are diethylaluminum hydride and diisobutylaluminum hydride.

(c) Transition Metal Compound

The transition metal compound of the 4 group metal of the periodic tableof the elements used in the present invention includes, for example,titanium compounds, zirconium compounds and hafnium compounds. Of these,titanium compounds, particularly those represented by the followingformula, are preferred,

Ti(OR)_(n)X_(4-n)

wherein R is an alkyl group having 1 to 4 carbon atoms, X is a chlorine,bromine or iodine atom, and n is 0 or an integer of 1 to 3.

Specific examples of the titanium compounds represented by the aboveformula are tetrahalogeno titanium compounds such as titaniumtetrachloride, titanium tetrabromide and titanium tetraiodide,trihalogeno alkoxytitanium compounds such as methoxytitaniumtrichloride, ethoxytitanium trichloride, butoxytitanium trichloride,phenoxytitanium trichloride and ethoxytitanium tribromide, dihalogenodialkoxytitanium compounds such as dimethoxytitanium dichloride,diethoxytitanium dichloride, dibutoxytitanium dichloride,diphenoxytitanium dichloride and diethoxytitanium dibromide,monohalogeno trialkoxytitanium compounds such as trimethoxytitaniumchloride, triethoxytitanium chloride, tributoxytitanium chloride,triphenoxytitanium chloride and triethoxytitanium bromide, andtetraalkoxytitanium compounds such as tetramethoxytitanium,tetraethoxytitanium and tetraphenoxytitanium. Of these, tetrahalogenotitanium compounds are preferred, and titanium tetrachloride isparticularly preferred.

(d) Phenol Compound

The phenol compound used in the present invention includes thosesubstituted or unsubstituted. Phenol compounds having a substituent atleast at 2-position are preferred, and those having substituents atleast at 2 and 6-positions are particularly preferred. Preferredsubstituents are a halogen atom and alkyl, aralkyl, aryl, silyl, alkoxy,aralkoxy, aryloxy and silyloxy groups, which are substituted orunsubstituted with a halogen atom.

Specific examples of the phenol compounds are 2-substituted phenols suchas 2-methylphenol, 2-ethylphenol, 2-n-butylphenol, 2-iso-butylphenol,2-t-butylphenol, 2-n-propylphenol, 2-iso-propylphenol, 2-phenylphenol,2-fluorophenol, 2-chlorophenol and 2-bromophenol, 2,6-substitutedphenols such as 2,6-dimethylphenol, 2,6-diethylphenol,2,6-di-n-butylphenol, 2,6-di-iso-butylphenol, 2,6-di-t-butylphenol,2,6-di-n-propylphenol, 2,6-di-iso-propylphenol, 2,6-diphenylphenol,2,6-difluorophenol, 2,6-dichlorophenol and 2,6-dibromophenol, and2,6,X-substituted phenols (X is a number selected from 3, 4 and 5) suchas 2,4,6-trimethylphenol, 2,6-di-t-butyl-4-methylphenol andpentafluorophenol.

Preferred phenol compounds are 2-methylphenol, 2-ethylphenol,2-n-butylphenol, 2-iso-butylphenol, 2-t-butylphenol, 2-n-propylphenol,2-iso-propylphenol, 2-phenylphenol, 2,6-dimethylphenol,2,6-diethylphenol, 2,6-di-n-butylphenol, 2,6-di-iso-butylphenol,2,6-di-t-butylphenol, 2,6-di-n-propylphenol, 2,6-di-iso-propylphenol and2,6-diphenyphenol.

More preferred phenol compounds are 2-, 2,6- or 2,6, X(X is as definedabove)-substituted phenols having a branch-carrying alkyl, cycloalkyl oraryl group.

(A) Solid Catalyst Component

The solid catalyst component for olefin polymerization in accordancewith the present invention is a solid catalyst component (A1) obtainedby contacting the carrier (a), the organometallic compound (b) and thetransition metal compound (c) with one another. Another solid catalystcomponent for olefin polymerization in accordance with the presentinvention is a solid catalyst component (A2) obtained by contacting thecarrier (a), the organometallic compound (b), the transition metalcompound (c) and the phenol compound (d) with one another. In the above,it is preferred to use the phenol compound (d) from a viewpoint ofdecreasing the production of the lower molecular weight components andthe low crystallinity components. The obtained solid catalyst componentis preferably stored in a cool and dark place under an inert gasatmosphere such as nitrogen and argon.

Contacting order of the components (a) to (d) is not limited. It isparticularly preferred to carry out a first contact of (a) with (b), anda second contact of the first contact product with (c), in this order.In case where (d) is used, it is particularly preferred to carry out afirst contact of (a) with (b), a second contact of the first contactproduct with (c), and a third contact of the second contact product with(d). These contacts may be carried out continuously or preferably in amanner such that the respective resulting products are washed with asolvent before subjecting to successive contact. Contacting time foreach contact is not particularly limited and usually from about 5minutes to 24 hours.

The contacts of respective components are preferably carried out in aslurry state in the presence of a solvent at a temperature, at which theshape of the carrier can be maintained, and under atmosphere of an inertgas such as nitrogen and argon. The temperature ranges usually fromabout −30 to 100° C., preferably from about 0 to 80° C., more preferablyfrom about 20 to 60° C. The solvent includes, for example, aliphatichydrocarbons such as pentane, hexane, heptane, octane and decane,aromatic hydrocarbons such as benzene, toluene and xylene, alicyclichydrocarbons such as cyclohexane and cyclopentane, halogeno hydrocarbonssuch as 1,2-dichloroethane and monochlorobenzene, and ether compoundssuch as diethyl ether, dibutyl ether, diisoamyl ether andtetrahydrofuran. Preferred solvents are aliphatic hydrocarbons andaromatic hydrocarbons, and more preferred are hexane, heptane, octane,toluene and xylene.

With respect to amounts of respective components, the amount of theorganometallic compound to be used is usually from about 0.1 to 100times, preferably from about 0.1 to 10 times, that of the carboxyl groupin the carrier in terms of a molar ratio, and the amount of thetransition metal compound to be used is usually from about 0.1 to 100times, preferably from about 0.1 to 10 times, that of the organometalliccompound in terms of a molar ratio. Moreover, the amount of the phenolcompound to be used is usually from about 0.1 to 100 times, preferablyfrom about 0.1 to 10 times, that of the transition metal compound fixedon the carrier.

(B) Organoaluminum Compound and Organoaluminumoxy Compound

The catalyst for olefin polymerization in accordance with the presentinvention is that obtained by using the solid catalyst component (A) asmentioned above and at least one compound (B) selected from the groupconsisting of organoaluminum compounds and organoaluminumoxy compounds.

The organoaluminum compounds are those having at least one Al—C bond inthe molecule, and, for example, represented by the following formula,

R⁴ _(n)AlZ_(3-n)

wherein R⁴ is an alkyl group having 1 to 10 carbon atoms, Z is a halogenor hydrogen atom, and n is a number satisfying 0<n≦3. Specific examplesthereof are trimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, tri-iso-butylaluminum, tri-tert-butylaluminum,tri-iso-propylaluminum, tripentylaluminum, tri-n-hexylaluminum,tri-(2-methylpentyl) aluminum, tri-n-octylaluminum, diethylaluminumhydride, di-iso-butylaluminum hydride, methylaluminum sesquichloride,ethylaluminum sesquichloride, isobutylaluminum sesquichloride,dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminumchloride, di-n-butylaluminum chloride, di-iso-butylaluminum chloride,di-tert-butylaluminum chloride, di-iso-propylaluminum chloride,di-pentylaluminum chloride, methylaluminum dichloride, ethylaluminumdichloride, isobutylaluminum dichloride, tert-butylaluminum dichloride,isopropylaluminum dichloride and pentylaluminum dichloride. Of these,diethylaluminum chloride, triethylaluminum and triisobutylaluminum arepreferably used.

As the organoaluminumoxy compounds, those known in the art as aluminoxancompounds can be used. For example, those obtained by the reactionbetween one kind of trialkylaluminum and water and those obtained bycondensation between two or more kinds of trialkylaluminum and water areused. Specific examples of the organoaluminumoxy compound aremethylaluminoxan, ethylaluminoxan, propylaluminoxan, butylaluminoxan,isobutylaluminoxan, methylethylaluminoxan, methylbutylaluminoxan andmethylisobutylaluminoxan. Of these, methylaluminoxan, isobutylaluminoxanand methylisobutylaluminoxan are particularly preferred.

The solid catalyst component for olefin polymerization used in thepresent invention may be those obtained through a pre-polymerization.The pre-polymerization can be carried out, for example, by contactingthe aforementioned solid catalyst component and organoaluminum compoundand an olefin with one another. The olefin includes, for example,ethylene, propylene and butene-1. The pre-polymerization may be eitherhomopolymerization or copolymerization.

In carrying out the pre-polymerization, the solid catalyst component ispreferably slurried with a solvent. The solvent includes, for example,aliphatic hydrocarbons such as butane, pentane, hexane and heptane, andaromatic hydrocarbons such as toluene and xylene.

In the pre-polymerization, it is preferred to use the organoaluminumcompound in a proportion of from about 0.1 to 100, preferably from about1 to 10, in terms of Al/Ti molar ratio. A pre-polymerization temperatureis from about −30 to 80° C., preferably from about −10 to 50° C., and apre-polymerization amount ranges from about 0.1 to 100 g, preferablyfrom about 0.5 to 50 g per g of the solid catalyst component

[Production of Olefin Polymer]

In the production process of an olefin polymer in accordance with thepresent invention, the solid catalyst component (A) subjected topre-polymerization, or not, and at least one compound (B) selected fromthe group consisting of the organoaluminum compounds and theorganoaluminumoxy compounds (hereinafter, referred to simply as theorganoaluminum compound (B)) are fed to a polymerization vessel. Thefeeding is, for example, carried out in a water-free state underatmosphere of an inert gas such as nitrogen and argon in the presence ofan olefin. Here, the solid catalyst component (A) and the organoaluminumcompound (B) may be fed thereto independently of each other, or they maybe contacted with each other in advance and then fed thereto. Inaddition, a chain transfer agent such as hydrogen can be added theretoto regulate a molecular weight of the olefin polymer.

An amount of the organoaluminum compound (B) in terms of mole of thealuminum atom contained therein is from about 1 to 10000 moles,preferably from about 1 to 3000 moles per mole of the transition metalatom contained in the solid catalyst component (A).

In producing the olefin polymer, a known electron donor and hydrogen maybe used. The electron donor includes, for example, an organic compoundhaving an Si—OR bond in the molecule, R being a hydrocarbon group having1 to 20 carbon atoms.

Specific examples of the Si—OR bond-carrying organic compound aretetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane,triethoxysilane, diethoxydiethylsilane, ethoxytriethylsilahe,tetra-iso-propoxysilane, di-iso-propoxy-di-iso-propylsilane,tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane,dibutoxydibutylsilane, dicyclopentoxydiethylsilane,diethoxydiphenylsilane, cyclohexyloxytrimethylsilane,phenoxytrimethylsilane, tetraphenoxysilane, triethoxyphenylsilane,hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane,octaethyltrisiloxane, poly(dimethylsiloxane), poly(diphenylsiloxane),poly(methylhydrosiloxane) and poly(phenylhydrosiloxane).

The olefin usable in the production process of the olefin polymer inaccordance with the present invention includes, for example, olefins anddiolefins having 2 to 20 carbon atoms. Two or more of these olefins canbe used simultaneously. Specific examples thereof are ethylene,propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1,decene-1,4-methyl-pentene-1 and vinylcyclohexene. A combination of anolefin with the other to obtain an olefin copolymer includes, forexample, ethylene with propylene, ethylene with butene-1, ethylene withhexene-1, ethylene with octene-1, and propylene with butene-1.

Preferred examples of the olefin polymer obtained by the productionprocess of the olefin polymer in accordance with the present inventionare copolymers of ethylene with α-olefins such as a copolymer ofethylene with propylene, a copolymer of ethylene with butene-1, acopolymer of ethylene with hexene-1 and a copolymer of ethylene withoctene-1

A polymerization temperature is usually from about −30 to 300° C.,preferably from about 20 to 250° C., more preferably from about 20 to100° C., providing that the temperature is not higher than that, atwhich the olefin polymer is melt. A polymerization pressure is notparticularly limited, and a pressure of from atmospheric pressure to 150atm. is preferred from an industrial and economical point of view. Apolymerization time can be determined generally depending on the kind ofthe polymer to be obtained and the reaction apparatus, and usuallyranges from about 5 minutes to 40 hours.

The polymerization process may be carried out as a continuous orbatchwise process. A slurry or solvent polymerization with use of inertsolvents such as propane, pentane, hexane, heptane and octane, and aliquid phase or vapor phase polymerization with use of no solvent can beapplied. The catalyst for the olefin polymerization in accordance withthe present invention is particularly suitable for a slurrypolymerization and a vapor phase polymerization.

According to the present invention by using a specific carrier ofcarboxyl group-carrying polymer particles, there can be provided a solidcatalyst component and catalyst for olefin polymerization, which arehigh in their polymerization activity and capable of producing an olefinpolymer extremely low in its content of lower molecular weightcomponents and low crystallinity components and superior in its powderproperties.

Further, according to the present invention, there can be provided aprocess for producing such a solid catalyst component with highefficiency, and a process for producing an olefin polymer with highefficiency, the polymer obtained being extremely low in its content oflower molecular weight components and low crystallinity components andsuperior in its powder properties.

The present invention is explained in more detail with reference to thefollowing Examples, which are only illustrative and not to be construedto limit the scope of the present invention. The measurement valuesrelating to particulars in the Examples were obtained in the followingmanners.

1. Ti content in catalyst

Measured according to ICP emission analysis using Optima 3000manufactured by Perkin Elmer Ltd.

2. Content of α-olefin

Measured from the absorption characteristics of ethylene and theα-olefin using an infrared spectrophotometer, IR-810, manufactured byJapan Spectroscopic Co., LTD., and expressed in terms of a short chainbranch number (SCB) per 1000 C (carbon atom).

3. Melt flow rate (MFR)

Measured at 190° C. according to ASTM D1238.

4. Melt flow rate ratio (MFRR)

MFRR was shown in terms of a ratio of the melt flow rate (MFR) measuredat 190° C. according to ASTM D1238 and that measured similarly,providing that the load applied was changed to 21.60 kg, namely,

MFRR=(melt flow rate when the load was 21.60 kg)÷(melt flow rate whenthe load was 2.160 kg).

5. Lower molecular weight components, low crystallinity components

Evaluated by a quantity (CXS, % by weight) of soluble portions when thepolymer was mixed with a cold xylene of 25° C. In general, the CXS valuetends to increase with an increase of the SCB value.

EXAMPLE 1

(1) Washing of Polymer Particles

In a 200 ml round bottom flask purged with nitrogen gas and equippedwith a stirrer, 10 g of an ethylene/acrylic acid copolymer (trade mark:FLOW BEADS, manufactured by Sumitomo Seika Chemicals Co., acrylic acidcontent: 7.0% by weight, average particle size: 26 μm, standarddeviation of particle distribution: 15 μm) and 100 ml of acetone werefed, and stirred for 10 minutes at room temperature. Thereafter, thepolymer particles were separated by filtration using a glass filter. Inthe round bottom flask, the polymer particles separated and 100 ml ofacetone were fed and treated again in the same manner as above. Thepolymer particles recovered were dried at 40° C. for 3 hours underreduced pressure. The amount of the polymer particles recovered wasalmost the same as the amount fed. It was microscopically confirmed thatthe shape of the polymer particles was maintained.

(2) Production of Solid Catalyst Component

In a 100 ml round bottle flask thoroughly purged with nitrogen gas andequipped with a stirrer, 2.0 g of the ethylene/acrylic acid copolymerwashed in the above (1) and 40 ml of n-hexane were fed, and 15 ml of an-hexane solution of 8.0 mmol of n-butylethylmagnesium was addeddropwise thereto over 15 minutes. The mixture was stirred at 40° C. for2 hours. After the reaction was over, the reaction mixture was filteredto separate a solid, which was washed twice with 40 ml of n-hexane.Successively, the solid was mixed with 40 ml of n-hexane, and a solutionof 2.2 ml of titanium tetrachloride in 15 ml of n-hexane was addeddropwise thereto. The mixture was stirred at 40° C. for 1 hour. Afterthe reaction was over, the reaction mixture was filtered to separate asolid, which was washed three times with 40 ml of n-hexane, andthereafter dried at room temperature for 2 hours under reduced pressure,thereby obtaining a solid catalyst component (I). The Ti content in thesolid catalyst component (I) was found to be 0.13 mmol/g. It wasmicroscopically confirmed that the shape of the polymer particles in thesolid catalyst component produced was maintained.

(3) Ethylene/butene-1 Copolymerization

A 400 ml stainless-made pressure reaction tube thoroughly purged withnitrogen gas and equipped with a stirrer was held in reduced pressure,and 20 g of butene-1 and 80 g of n-butane were fed therein. Thetemperature in the system was raised to 70° C., and then 2.5 kg/cm² ofhydrogen and 6 kg/cm² of ethylene were fed therein. The mixture wasstirred for a while until the system reached saturation. A solutionprepared by dissolving 1.0 mmol of triisobutylaluminum in 1.0 ml ofn-heptane and a solution prepared by suspending 14.6 mg of the solidcatalyst component (I) obtained above in 5 ml of n-heptane were fed inthis order under a pressure of argon to initiate polymerization. Onehour after, ethanol was fed in the reaction system to discontinue thepolymerization, and unreacted gases were purged to recover a copolymer.The copolymer recovered was dried at 60° C. for 4 hours under reducedpressure to obtain 14.3 g of ethylene/butene-1 copolymer. With respectto the copolymer obtained, SCB, MFR, MFRR and CXS were found to be 21.33(/1000C), 2.26 (g/10 min.), 29.1 and 7.6 wt %, respectively. It wasmicroscopically confirmed that the copolymer obtained was spherical likethe solid catalyst component used, narrow in its particle distributionand superior in its powder properties.

EXAMPLE 2

(1) Production of Solid Catalyst Component

In a 100 ml round bottle flask thoroughly purged with nitrogen gas andequipped with a stirrer, 2.0 g of the ethylene/acrylic acid copolymerwashed in Example 1 (1) and 40 ml of n-hexane were fed, and 15 ml of an-hexane solution of 8.0 mmol of n-butylethylmagnesium was addeddropwise thereto over 15 minutes. The mixture was stirred at 40° C. for2 hours. After the reaction was over, the reaction mixture was filteredto separate a solid, which was washed twice with 40 ml of n-hexane.Successively, the solid was mixed with 40 ml of n-hexane, and a solutionof 2.2 ml of titanium tetrachloride in 15 ml of n-hexane was addeddropwise thereto. The mixture was stirred at 60° C. for 1 hour. Afterthe reaction was over, the reaction mixture was filtered to separate asolid, which was washed three times with 40 ml of hexane, and thereafterdried at room temperature for 2 hours under reduced pressure, therebyobtaining a solid catalyst component (II). The Ti content in the solidcatalyst component (II) was found to be 0.1 mmol/g.

(2) Ethylene/butene-1 Copolymerization

Example 1 (3) was repeated, except that the amount of hydrogen waschanged to 2 kg/cm², and 12.1 mg of the solid catalyst component (II)was used in place of the solid catalyst component (I).

As a result, 5.8 g of ethylene/butene-1 copolymer was obtained. Withrespect to the copolymer obtained, SCB, MFR, MFRR and CXS were found tobe 17.91 (/1000C), 0.98 (g/10 min.), 27.2 and 4.9 wt %, respectively.The powder properties of the copolymer obtained were found to besuperior.

EXAMPLE 3

(1) Production of Solid Catalyst Component

In a 300 ml round bottle flask thoroughly purged with nitrogen gas andequipped with a stirrer, 6.0 g of the ethylene/acrylic acid copolymerprepared in Example 1 (1) and 120 ml of n-heptane were fed, and 30 ml ofa n-heptane solution of 24.0 mmol of n-butylethylmagnesium was addeddropwise thereto over 30 minutes. The mixture was stirred at 40° C. for2 hours. After the reaction was over, the reaction mixture was filteredto separate a solid, which was washed three times with 100 ml ofn-heptane. Successively, the solid was mixed with 120 ml of n-heptane,and a solution of 6.6 ml of titanium tetrachloride in 20 ml of n-heptanewas added dropwise thereto over 30 minutes. The mixture was stirred atroom temperature for 1 hour. After the reaction was over, the reactionmixture was filtered to separate a solid, which was washed three timeswith 100 ml of hexane, and thereafter dried at room temperature for 2hours under reduced pressure, thereby obtaining a solid catalystcomponent (III).

(2) Ethylene/butene-1 Copolymerization

Example 1(3) was repeated, except that the amounts of butene-1, n-butaneand hydrogen were changed to 23 g, 77 g and 2 kg/cm², respectively, and8.6 mg of the solid catalyst component (III) was used in place of thesolid catalyst component (I).

As a result, 6.4 g of ethylene/butene-1 copolymer was obtained. Withrespect to the copolymer obtained, SCB, MFR, MFRR and CXS were found tobe 19.70 (/1000C), 0.54 (g/10 min.), 29.0 and 6.8 wt %, respectively.The powder properties of the copolymer obtained were found to besuperior.

EXAMPLE 4

(1) Washing of Polymer Particles

A washing treatment was carried out according to Example 1 (1), exceptthat an ethylene/acrylic acid copolymer having an average particle sizeof 25 μm and a standard deviation of particle distribution of 15 μm(trade mark: FLOW BEADS, manufactured by Sumitomo Seika Chemicals Co.,acrylic acid content: 7.0% by weight) was used.

(2) Production of Solid Catalyst Component

In a 100 ml round bottle flask thoroughly purged with nitrogen gas andequipped with a stirrer, 2.06 g of the ethylene/acrylic acid copolymerwashed in the above (1) and 41 ml of n-heptane were fed, and 20 ml of an-heptane solution of 8.24 mmol of n-butylethylmagnesium was addeddropwise thereto over 20 minutes. The mixture was stirred at 40° C. for2 hours. After the reaction was over, the reaction mixture was filteredto separate a solid, which was washed three times with 40 ml ofn-heptane. Successively, the solid was mixed with 41 ml of n-heptane,and a solution of 2.27 ml of titanium tetrachloride in 15 ml of n-hexanewas added dropwise thereto. The mixture was stirred at room temperaturefor 1 hour. After the reaction was over, the reaction mixture wasfiltered to separate a solid, which was washed three times with 40 ml ofhexane, and thereafter dried at room temperature for 2 hours underreduced pressure, thereby obtaining a solid catalyst component (IV). ATi content in the solid catalyst component (IV) was found to be 0.18mmol/g.

(3) Ethylene/butene-1 Copolymerization

Example 1 (3) was repeated, except that the amount of hydrogen waschanged to 2.5 kg/cm², and 13.1 mg of the solid catalyst component (IV)was used in place of the solid catalyst component (I).

As a result, 6.0 g of ethylene/butene-1 copolymer was obtained. Withrespect to the copolymer obtained, SCB, MFR, MFRR and CXS were found tobe 17.46 (/1000C), 0.42 (g/10 min.), 34 and 4.5 wt %, respectively. Thepowder properties of the copolymer obtained were found to be superior.

EXAMPLE 5

(1) Washing of Polymer Particles

A washing treatment was carried out according to Example 1 (1), exceptthat an ethylene/acrylic acid copolymer having an average particle sizeof 11 μm and a standard deviation of particle distribution of 5 μm(trade mark: FLOW BEADS, manufactured by Sumitomo Seika Chemicals Co.,acrylic acid content: 7.0% by weight) was used.

(2) Production of Solid Catalyst Component

In a 100 ml round bottle flask thoroughly purged with nitrogen gas andequipped with a stirrer, 2.0 g of the ethylene/acrylic acid copolymerwashed in the above (1) and 40 ml of n-heptane were fed, and 10 ml of an-heptane solution of 8.0 mmol of n-butylethylmagnesium was addeddropwise thereto at 0 to 5° C. over 30 minutes. The mixture was stirredat 40° C. for 2 hours. After the reaction was over, the reaction mixturewas filtered to separate a solid, which was washed three times with 40ml of n-heptane. Successively, the solid was mixed with 40 ml ofn-heptane, and a solution of 2.2 ml of titanium tetrachloride in 10 mlof n-heptane was added dropwise thereto. The mixture was stirred at roomtemperature for 1 hour. After the reaction was over, the reactionmixture was filtered to separate a solid, which was washed three timeswith 50 ml of hexane, and thereafter dried at room temperature for 2hours under reduced pressure, thereby obtaining a solid catalystcomponent (V). The Ti content in the solid catalyst component (V) wasfound to be 0.41 mmol/g.

(3) Ethylene/butene-1 Copolymerization

Example 1 (3) was repeated, except that the amount of hydrogen waschanged to 1.5 kg/cm² and 5.6 mg of the solid catalyst component (V) wasused in place of the solid catalyst component (I).

As a result, 8.5 g of ethylene/butene-1 copolymer was obtained. Withrespect to the copolymer obtained, SCB, MFR, MFRR and CXS were found tobe 18.19 (/1000C), 0.80 (g/10 min.), 28.1 and 5.5 wt %, respectively.The powder properties of the copolymer obtained were found to besuperior.

EXAMPLE 6

(1) Production of Solid Catalyst Component

In a 100 ml round bottle flask thoroughly purged with nitrogen gas andequipped with a stirrer, 2.25 g of the ethylene/acrylic acid copolymerprepared in Example 5 (1) and 45 ml of n-heptane were fed, and 10 ml ofa n-heptane solution of 9.0 mmol of n-butylethylmagnesium was addeddropwise thereto at room temperature over 30 minutes. The mixture wasstirred at 40° C. for 2 hours. After the reaction was over, the reactionmixture was filtered to separate a solid, which was washed three timeswith 50 ml of n-heptane. Successively, the solid was mixed with 45 ml ofn-heptane, and a solution of 2.48 ml of titanium tetrachloride in 10 mlof n-heptane was added dropwise thereto. The mixture was stirred at roomtemperature for 1 hour. After the reaction was over, the reactionmixture was filtered to separate a solid, which was washed three timeswith 50 ml of hexane, and thereafter dried at room temperature for 2hours under reduced pressure, thereby obtaining a solid catalystcomponent (VI). The Ti content in the solid catalyst component (VI) wasfound to be 0.43 mmol/g.

(2) Ethylene/butene-1 Copolymerization

Example 1 (3) was repeated, except that the amount of hydrogen waschanged to 1.5 kg/cm², and 4.5 mg of the solid catalyst component (VI)was used in place of the solid catalyst component (I).

As a result, 9.5 g of ethylene/butene-1 copolymer was obtained. Withrespect to the copolymer obtained, SCB, MFR, MFRR and CXS were found tobe 17.44 (/1000C), 0.74 (g/10 min.), 27.8 and 4.8 wt %, respectively.The powder properties of the copolymer obtained were found to besuperior.

EXAMPLE 7

(1) Production of Solid Catalyst Component

In a 300 ml round bottle flask thoroughly purged with nitrogen gas andequipped with a stirrer, 8.2 g of the ethylene/acrylic acid copolymerwashed in a manner similar to that of Example 5 (1) and 164 ml ofn-heptane were fed, and 25 ml of a n-heptane solution of 32.8 mmol ofn-butylethylmagnesium was added dropwise thereto at room temperatureover 10 minutes. The mixture was stirred at 40° C. for 2 hours. Afterthe reaction was over, the reaction mixture was filtered to separate asolid, which was washed three times with 160 ml of n-heptane.Successively, the solid was mixed with 164 ml of n-heptane, and asolution of 9.02 ml of titanium tetrachloride in 20 ml of n-heptane wasadded dropwise thereto. The mixture was stirred at room temperature for1 hour. After the reaction was over, the reaction mixture was filteredto separate a solid, which was washed three times with 160 ml of hexane,and thereafter dried at room temperature for 2 hours under reducedpressure, thereby obtaining a solid. The Ti content in the solid wasfound to be 0.23 mmol/g.

In a 300 ml round bottle flask thoroughly purged with nitrogen gas andequipped with a stirrer, 8.9 g of the above solid and 178 ml ofn-heptane were fed. Successively, 63 μl of 2-tert-butylphenol was fedtherein, and the mixture was stirred at room temperature for 1 hours.After the reaction was over, the reaction mixture was filtered toseparate a solid, which was washed three times with 50 ml of n-hexane,and thereafter dried at room temperature for 2 hours under reducedpressure, thereby obtaining a solid catalyst component (VII). The Ticontent in the solid catalyst component (VII) was found to be 0.16mmol/g.

(2) Ethylene/butene-1 Copolymerization

Example 1 (3) was repeated, except that the amount of hydrogen waschanged to 2.0 kg/cm², and 5.9 mg of the solid catalyst component (VII)was used in place of the solid catalyst component (I).

As a result, 4.4 g of ethylene/butene-1 copolymer was obtained. Withrespect to the copolymer obtained, SCB, MFR, MFRR and CXS were found tobe 23.20 (/1000C), 1.0 (g/10 min.), 27 and 7.4 wt %, respectively. Thepowder properties of the copolymer obtained were found to be superior.

EXAMPLE 8

(1) Production of Solid Catalyst Component

In a 500 ml round bottle flask thoroughly purged with nitrogen gas andequipped with a stirrer, 11.8 g of the ethylene/acrylic acid copolymerwashed in a manner similar to that of Example 5 (1) and 236 ml ofn-heptane were fed, and 60 ml of a n-heptane solution of 47.2 mmol ofn-butylethylmagnesium was added dropwise thereto at room temperatureover 45 minutes. The mixture was stirred at 40° C. for 2 hours. Afterthe reaction was over, the reaction mixture was filtered to separate asolid, which was washed once with 200 ml of n-heptane and additionallytwo times with 200 ml of toluene. Successively, the solid was mixed with236 ml of toluene, and a solution of 13 ml of titanium tetrachloride in50 ml of toluene was added dropwise thereto over 45 minutes. The mixturewas stirred at room temperature for 1 hour. After the reaction was over,the reaction mixture was filtered to separate a solid, which was washedonce with 50 ml of toluene, and additionally twice with hexane, andthereafter dried at room temperature for 2 hours under reduced pressure,thereby obtaining a solid catalyst component (VIII). The Ti content inthe solid catalyst component (VIII) was found to be 0.26 mmol/g.

In a 300 ml round bottle flask thoroughly purged with nitrogen gas andequipped with a stirrer, 1.27 g of the above solid catalyst component(VIII) and 60 ml of n-heptane were fed. Successively, 25.2 μl of2-tert-butylphenol was fed therein, and the mixture was stirred at roomtemperature for 1 hour. After the reaction was over, the reactionmixture was filtered to separate a solid, which was washed three timeswith 50 ml of n-hexane, and thereafter dried at room temperature for 2hours under reduced pressure, thereby obtaining a solid catalystcomponent (IX). A Ti content in the solid catalyst component (IX) wasfound to be 0.38 mol/g.

(2) Ethylene/butene-1 Copolymerization (1)

Example 1 (3) was repeated, except that the amounts of butene-1,n-butane and hydrogen were changed to 22 g, 78 g and 2.0 kg/cm²,respectively, and 13.5 mg of the solid catalyst component (VIII) wasused in place of the solid catalyst component (I).

As a result, 9.8 g of ethylene/butene-1 copolymer was obtained. Withrespect to the copolymer obtained, SCB, MFR, MFRR and CXS were found tobe 17.87 (/1000C), 1.16 (g/10 min.), 28.6 and 4.8 wt %, respectively.The powder properties of the copolymer obtained were found to besuperior.

(3) Ethylene/butene-1 Copolymerization (2)

Example 1 (3) was repeated, except that the amounts of butene-1,n-butane and hydrogen were changed to 22 g, 78 g and 2.0 kg/cm²,respectively, and 8.2 mg of the solid catalyst component (IX) was usedin place of the solid catalyst component (I).

As a result, 5.2 g of ethylene/butene-1 copolymer was obtained. Withrespect to the copolymer obtained, SCB, MFR, MFRR and CXS were found tobe 19.20 (/1000C), 0.83 (g/10 min.), 25.6 and 3.9 wt %, respectively.The powder properties of the copolymer obtained were found to besuperior.

COMPARATIVE EXAMPLE 1

(1) Washing of Polymer Particles

In a 2 liter round bottle separable flask, 10 g of an ethylene/acrylicacid copolymer (average particle size: 28 μm, standard deviation ofparticle distribution: 15 μm, trade mark: FLOW BEADS, manufactured bySumitomo Seika Chemicals Co., acrylic acid content: 7.0% by weight,) and1 liter of xylene were fed, and refluxed for 6 hours under heating todissolve the copolymer. Two liters of methanol were placed in advance ina mixer, and a half 500 ml of the resulting xylene solution and theremaining half thereof were dividedly introduced in the methanol in ahot state. The resulting slurry of polymer fine powder was filtered witha Buchner funnel, and the polymer fine powder recovered was placed in a500 ml round bottom flask purged with nitrogen gas. 200 ml of driedacetone was added thereto, and the mixture was stirred at roomtemperature for 10 minutes. The acetone slurry was filtered to separatewhite fine particles of the polymer. In the round bottom flask, thepolymer particles separated and 200 ml of acetone were fed and treatedagain in the same manner as above. The polymer particles recovered weredried at 40° C. for 3 hours under reduced pressure.

(2) Production of Solid Catalyst Component

In a 100 ml round bottle flask thoroughly purged with nitrogen gas andequipped with a stirrer, 1.9 g of the ethylene/acrylic acid copolymerprepared in the above step and 38 ml of n-heptane were fed, and 15 ml ofa n-heptane solution of 7.6 mmol of n-butylethylmagnesium was addeddropwise thereto over 15 minutes. The mixture was stirred at 40° C. for2 hours. After the reaction was over, the reaction mixture was filteredto separate a solid, which was washed three times with 40 ml ofn-heptane. Successively, the solid was mixed with 40 ml of n-heptane,and a solution of 2.1 ml of titanium tetrachloride in 20 ml of n-heptanewas added dropwise thereto over 15 minutes. The mixture was stirred atroom temperature for 1 hour. After the reaction was over, the reactionmixture was filtered to separate a solid, which was washed three timeswith 40 ml of n-hexane, and thereafter dried at room temperature for 2hours under reduced pressure, thereby obtaining a solid catalystcomponent (A). The Ti content in the solid catalyst component (A) wasfound to be 5.33 mmol/g.

(3) Ethylene/butene-1 Copolymerization

Example 1 (3) was repeated, except that the amounts of butene-1,n-butane and hydrogen were changed to 15 g, 85 g and 1.5 kg/cm², and 1.6mg of the solid catalyst component (A) was used in place of the solidcatalyst component (I).

As a result, 19.8 g of ethylene/butene-1 copolymer was obtained. Withrespect to the copolymer obtained, SCB, MFR, MFRR and CXS were found tobe 15.8 (/1000C), 0.58 (g/10 min.), 33.2 and 6.8 wt %, respectively. Itwas microscopically confirmed that the resulting copolymer had anon-spherical shape having fine whiskers, and the powder propertiesthereof were found to be not superior.

COMPARATIVE EXAMPLE 2

(1) Production of Solid Catalyst Component

In a 100 ml round bottle flask thoroughly purged with nitrogen gas andequipped with a stirrer, 1.75 g of the ethylene/acrylic acid copolymerprepared in Comparative Example 1 (1) and 35 ml of n-heptane were fed,and 15 ml of a n-heptane solution of 0.7 mmol of n-butylethylmagnesiumwas added dropwise thereto at room temperature over 15 minutes. Themixture was stirred at 40° C. for 2 hours. After the reaction was over,the reaction mixture was filtered to separate a solid, which was washedthree times with 40 ml of n-heptane. Successively, the solid was mixedwith 35 ml of n-heptane, and a solution of 0.19 ml of titaniumtetrachloride in 10 ml of n-heptane was added dropwise thereto over 15minutes. The mixture was stirred at room temperature for 1 hour. Afterthe reaction was over, the reaction mixture was filtered to separate asolid, which was washed three times with 40 ml of n-hexane, andthereafter dried at room temperature for 2 hours under reduced pressure,thereby obtaining a solid catalyst component (B). The Ti content in thesolid catalyst component (B) was found to be 0.53 mmol/g.

(2) Ethylene/butene-1 Copolymerization

Example 1 (3) was repeated, except that the amounts of butene-1,n-butane and hydrogen was changed to 18 g, 82 g and 1.2 kg/cm², and 2.4mg of the solid catalyst component (B) was used in place of the solidcatalyst component (I).

As a result, 7.3 g of ethylene/butene-1 copolymer was obtained. Withrespect to the copolymer obtained, SCB, MFR, MFRR and CXS were found tobe 18.59 (/1000C), 1.68 (g/10 min.), 29.4 and 6.9 wt %, respectively.

COMPARATIVE EXAMPLE 3

(1) Washing of Polymer Particles

The washing was carried out according to Comparative Example 1 (1),except that an ethylene/acrylic acid copolymer having an averageparticle size of 11 μm and a standard deviation of particle distributionof 5 μm, (trade mark: FLOW BEADS, manufactured by Sumitomo SeikaChemicals Co., acrylic acid content: 7.0% by weight,) were used.

(2) Production of Solid Catalyst Component

In a 100 ml round bottle flask thoroughly purged with nitrogen gas andequipped with a stirrer, 2.0 g of the ethylene/acrylic acid copolymerprepared in the above step and 40 ml of n-heptane were fed, and 15 ml ofa n-heptane solution of 8.0 mmol of n-butylethylmagnesium was addeddropwise thereto at room temperature over 15 minutes. The mixture wasstirred at 40° C. for 2 hours. After the reaction was over, the reactionmixture was filtered to separate a solid, which was washed three timeswith 40 ml of n-heptane. Successively, the solid was mixed with 40 ml ofn-heptane, and a solution of 2.2 ml of titanium tetrachloride in 15 mlof n-heptane was added dropwise thereto over 15 minutes. The mixture wasstirred at room temperature for 1 hour. After the reaction was over, thereaction mixture was filtered to separate a solid, which was washedthree times with 40 ml of n-hexane, and thereafter dried at roomtemperature for 2 hours under reduced pressure, thereby obtaining asolid catalyst component (C). The Ti content in the solid catalystcomponent (C) was found to be 5.12 mmol/g.

(3) Ethylene/butene-1 Copolymerization

Example 1 (3) was repeated, except that the amounts of butene-1,n-butane and hydrogen were changed to 17 g, 83 g and 1.8 kg/cm², and 2.3mg of the solid catalyst component (C) was used in place of the solidcatalyst component (I).

As a result, 21 g of ethylene/butene-1 copolymer was obtained. Withrespect to the copolymer obtained, SCB, MFR, MFRR and CXS were found tobe 22.26 (/1000C), 3.08 (g/10 min.), 33.9 and 12.8 wt %, respectively.

EXAMPLE 9

(1) Production of Solid Catalyst Component

In a 100 ml round bottle flask thoroughly purged with nitrogen gas andequipped with a stirrer, 2.0 g of an ethylene/acrylic acid copolymerhaving an average particle size of 28 μm and a standard deviation ofparticle distribution of 15 μm, (trade mark: FLOW BEADS, manufactured bySumitomo Seika Chemicals Co., acrylic acid content: 7.0% by weight,) and40 ml of n-heptane were fed, and 15 ml of a n-heptane solution of 8.0mmol of n-butylethylmagnesium was added dropwise thereto at roomtemperature over 30 minutes. The mixture was stirred at 40° C. for 2hours. After the reaction was over, the reaction mixture was filtered toseparate a solid, which was washed three times with 40 ml of n-heptane.Successively, the solid was mixed with 40 ml of n-heptane, and asolution of 2.2 ml of titanium tetrachloride in 20 ml of n-heptane wasadded dropwise thereto. The mixture was stirred at room temperature for1 hour. After the reaction was over, the reaction mixture was filteredto separate a solid, which was washed three times with 40 ml of hexane,and thereafter dried at room temperature for 2 hours under reducedpressure, thereby obtaining a solid catalyst component (X). A Ti contentin the solid catalyst component (X) was found to be 0.15 mmol/g.

(2) Ethylene/butene-1 Copolymerization

Example 1 (3) was repeated, except that the amounts of butene-1,n-butane and hydrogen were changed to 22 g, 78 g and 2.0 kg/cm², and25.5 mg of the solid catalyst component (X) was used in place of thesolid catalyst component (I).

As a result, 9.2 g of ethylene/butene-1 copolymer was obtained. Withrespect to the copolymer obtained, SCB, MFR, MFRR and CXS were found tobe 17.92 (/1000C), 0.64 (g/10 min.), 30.7 and 4.9 wt %, respectively.The powder properties of the copolymer obtained were found to besuperior.

What is claimed is:
 1. A catalytic process for producing an olefinpolymer, which comprises reacting together monomers of an olefin, adiolefin or a mixture thereof in the presence of a catalyst obtained bycombining a solid catalyst component (A1) and at least one compound (B)selected from the group consisting of organoaluminum compounds andorganoaluminumoxy compounds; wherein the solid catalyst component (A1)is obtained by contacting: (a) a carrier comprising carboxylgroup-carrying polymer particles of spherical or elliptical shape havingan average particle size of from about 1 to 200 μm and a standarddeviation of particle size distribution of from about 1 to about 30 μm,(b) an organometallic compound of the number 1, 2 or 13 group of metalsin the periodic table of elements, and (c) a transition metal compoundof the number 4 group of metals in the periodic table of elements. 2.The process according to claim 1, wherein the olefin polymer is acopolymer obtained by polymerizing an ethylene monomer with an α-olefinmonomer.
 3. A catalytic process for producing an olefin polymer, whichcomprises reacting together monomers of an olefin, a diolefin or amixture thereof in the presence of a catalyst obtained by combining asolid catalyst component (A2) and at least one compound (B) selectedfrom the group consisting of organoaluminum compounds andorganoaluminumoxy compounds; wherein the solid catalyst component (A2)is obtained by contacting: (a) a carrier comprising carboxylgroup-carrying polymer particles of spherical or elliptical shape havingan average particle size of from about 1 to 200 μm and a standarddeviation of particle size distribution of from about 1 to about 30 μm,(b) an organometallic compound of the number 1, 2 or 13 group of metalsin the periodic table of elements, (c) a transition metal compound ofthe number 4 group of metals in the periodic table of elements, and (d)a phenol compound.
 4. The process according to claim 3, wherein theolefin polymer is a copolymer obtained by polymerizing an ethylenemonomer with an α-olefin monomer.